Field of the Invention
The present invention relates to a process for preparing zeolites using quaternary ammonium cations as a structure directing agent (SDA).
In accordance with the present invention, there is provided a process for preparing a zeolite which comprises:
(a) preparing an aqueous solution from (1) sources of an alkali metal oxide, alkaline earth metal oxide or mixtures thereof, (2) sources of an oxide selected from oxides of silicon, germanium or mixtures thereof, (3) sources of an oxide selected from the oxides of aluminum, boron, iron, gallium, indium, titanium, vanadium or mixtures thereof, and (4) at least one quaternary ammonium cation capable of forming the zeolite having the formula 
xe2x80x83wherein:
X is xe2x80x94H, methyl, xe2x80x94F, xe2x80x94Cl, xe2x80x94F and xe2x80x94Cl, or methoxy;
R1 and R2 are each methyl or ethyl; R1 and R2 together are xe2x80x94(CH2)xxe2x80x94 where x is 2, 3, 4, or 5; or R1 and R2 together are methylated or dimethylatedxe2x80x94(CH2)yxe2x80x94 where y is 3, 4, or 5; and
R3, R4 and R5 are each methyl or ethyl, or one of R3, R4 or R5 is methyl and the other two together are xe2x80x94(CH2)zxe2x80x94 where z is 4, 5, 6 or 7;
(b) maintaining the aqueous solution under conditions sufficient to form crystals of the zeolite; and
(c) recovering the crystals of the zeolite.
The present invention also provides this process further comprising replacing alkali and/or alkaline earth metal cations of the recovered zeolite, at least in part, by ion exchange with a cation or mixture of cations selected from the group consisting of hydrogen and hydrogen precursors, rare earth metals, and metals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the Periodic Table of Elements.
The present invention also provides a zeolite composition, as-synthesized and in the anhydrous state, whose general composition, in terms of mole ratios, is as follows:
YO2/WcOdxe2x89xa720
Q/YO2 0.02-0.10
M2/n/YO2 0.01-0.10
wherein Y is silicon, germanium or a mixture thereof; W is aluminum, boron, gallium, indium, iron, titanium, vanadium or mixtures thereof; c is 1 or 2; d is 2 when c is 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when W is pentavalent); Q is at least one quaternary ammonium cation capable of forming the zeolite and having formula (I) above; M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; and n is the valence of M (i.e., 1 or 2).
The present invention comprises:
(a) preparing an aqueous solution from sources of oxides capable of forming a zeolite and at least one quaternary ammonium cation capable of forming the zeolite and having formula (I) above;
(b) maintaining the aqueous solution under conditions sufficient to form crystals of the zeolite; and
(c) recovering the crystals of the zeolite.
The process of the present invention comprises forming a reaction mixture from sources of alkali and/or alkaline earth metal (M) cations with valences n (i.e., 1 or 2); sources of an oxide of aluminum, boron, iron, gallium, indium, titanium, vanadium or mixtures thereof (W); sources of an oxide of silicon, germanium or mixtures thereof (Y); at least one quaternary ammonium cation of this invention (Q); and water, said reaction mixture having a composition in terms of mole ratios within the following ranges:
where Y, W, Q, M and n are as defined above, and a is 1 or 2, and b is 2 when a is 1 (i.e., W is tetravalent) and b is 3 when a is 2 (i.e., W is trivalent).
Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, hydrated aluminum hydroxides, and aluminum compounds such as AlCl3 and Al2(SO4)3. Typical sources of silicon oxide include silica hydrogel, silicic acid, colloidal silica, tetraalkyl orthosilicates, silica hydroxides, and fumed silicas. Gallium, iron, boron, indium, titanium, vanadium and germanium can be added in forms corresponding to their aluminum and silicon counterparts. Trivalent elements stabilized on silica colloids are also useful reagents.
The quaternary ammonium cations useful in the practice of this invention are those which are capable of forming a zeolite. The quaternary ammonium cations of this invention are represented by the following formula: 
wherein:
X is xe2x80x94H, methyl, xe2x80x94F, xe2x80x94Cl, xe2x80x94F and xe2x80x94Cl, or methoxy;
R1 and R2 are each methyl or ethyl; R1 and R2 together are xe2x80x94(CH2)xxe2x80x94 where x is 2, 3, 4, or 5; or R1 and R2 together are methylated or dimethylated xe2x80x94(CH2)yxe2x80x94 where y is 3, 4, or 5; and R3, R4 and R5 are each methyl or ethyl, or one of R3, R4 or R5 is methyl and the other two together are xe2x80x94(CH2)zxe2x80x94 where z is 4, 5, 6 or 7.
In preparing the zeolites in accordance with the present invention, the reactants and the SDA are dissolved in water and the resulting reaction mixture is maintained at an elevated temperature until crystals are formed. The hydrothermal crystallization is usually conducted under autogenous pressure, at a temperature between 100xc2x0 C. and 200xc2x0 C., preferably between 135xc2x0 C. and 160xc2x0 C. The crystallization period is typically greater than 1 day and preferably from about 3 days to about 20 days.
The hydrothermal crystallization is usually conducted under pressure and usually in an autoclave so that the reaction mixture is subject to autogenous pressure. The reaction mixture should be stirred during crystallization.
Once the crystals have formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques, such as filtration. The crystals are water-washed and then dried, e.g., at 90xc2x0 C. to 150xc2x0 C. for from 8 to 24 hours, to obtain the as-synthesized zeolite crystals. The drying step can be performed at atmospheric or subatmospheric pressures.
During the hydrothermal crystallization step, the crystals can be allowed to nucleate spontaneously from the reaction mixture. The reaction mixture can also be seeded with crystals of the desired zeolite both to direct, and accelerate the crystallization, as well as to minimize the formation of any undesired crystalline phases. When seed crystals are used, typically about 0.5% to about 5.0% by weight (based on the weight of silica used in the reaction mixture) of the seed crystals are added.
Due to the unpredictability of the factors which control nucleation and crystallization in the art of crystalline oxide synthesis, not every combination of reagents, reactant ratios, and reaction conditions will result in crystalline products. Selecting crystallization conditions which are effective for producing crystals may require routine modifications to the reaction mixture or to the reaction conditions, such as temperature, and/or crystallization time. Making these modifications are well within the capabilities of one skilled in the art.
The zeolite products made by the process of this invention have an as-synthesized composition comprising, in terms of mole ratios in the anhydrous state, the following:
YO2/WcOdxe2x89xa720
Q/YO2 0.02-0.10
M2/n/YO2 0.01-0.10
wherein Y, W, c, d, Q, M and n are as defined above. Preferably, Y is silicon, W is aluminum, and M is sodium.
The zeolite products made in accordance with this invention were identified by their X-ray diffraction (XRD) pattern. The X-ray powder diffraction patterns were determined by standard techniques. The radiation was the K-alpha/doublet of copper. In the X-ray data shown below, the peak heights I and the positions, as a function of 2 theta where theta is the Bragg angle, were read from the relative intensities, 100xc3x97I/I0 where I0 is the intensity of the strongest line or peak, and d, the interplanar spacing in Angstroms corresponding to the recorded lines, can be calculated.
The SDA""s of this invention can be used to prepare a variety of zeolites, including ZSM-5, ZSM-12, ZSM-39, ZSM-48, ZSM-51, SSZ-48, SSZ-53, SSZ55, and SSZ-59. Table A below shows the zeolites that have been made using the quaternary ammonium cations of this invention, as well as the particular cations that can be used to make each zeolite. It should be noted that in Table A, xe2x80x9cMexe2x80x9d represents a methyl group and the positive charge on the nitrogen atom is not shown.
ZSM-5 is a well known zeolite. It is disclosed in Szostak, xe2x80x9cHandbook of Molecular Sievesxe2x80x9d, Van Nostrand Reinhold, 1992 and in U.S. Pat. No. 3,702,886 (issued Nov. 14, 1972 to Argauer et al.), both of which are incorporated herein by reference in their entirety.
ZSM-12 is another well known zeolite. It is disclosed in Szostak, xe2x80x9cHandbook of Molecular Sievesxe2x80x9d, Van Nostrand Reinhold, 1992 and in U.S. Pat. No. 3,832,449 (issued Aug. 27, 1974 to Rosinski et al.), both of which are incorporated herein by reference in their entirety.
ZSM-39 is also a known zeolite. It is disclosed in Szostak, xe2x80x9cHandbook of Molecular Sievesxe2x80x9d, Van Nostrand Reinhold, 1992 and in U.S. Pat. No. 4,287,166 (issued Sep. 1, 1981 to Dweyer et al.), both of which are incorporated herein by reference in their entirety.
ZSM-48 is also a known zeolite. It is disclosed in Szostak, xe2x80x9cHandbook of Molecular Sievesxe2x80x9d, Van Nostrand Reinhold, 1992 and in U.S. Pat. No. 4,397,827 (issued Aug. 9, 1983 to Chu), both of which are incorporated herein by reference in their entirety.
ZSM-51 is also a known zeolite. It is disclosed in Szostak, xe2x80x9cHandbook of Molecular Sievesxe2x80x9d, Van Nostrand Reinhold, 1992 and in U.S. Pat. No. 4,568,654 (issued Feb. 4, 1986 to Valyocsik), both of which are incorporated herein by reference in their entirety.
Zeolite SSZ-48 is a known zeolite. It is disclosed in U.S. Pat. No. 6,080,382 (issued Jun. 27, 2000 to Lee et al.) which is incorporated herein by reference in its entirety.
SSZ-53 is disclosed in copending U.S. patent application Ser. No. 09/836,923, filed Apr. 17, 2001, which is a continuation-in-part of Ser. No. 09/584,187, filed May 31, 2000. Both applications are incorporated herein by reference in their entirety.
SSZ-53 is prepared from a reaction mixture having the composition shown in Table 1 below.
where Y is silicon, germanium or a mixture thereof; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M (i.e., 1 or 2); a is 1 or 2, and b is 2 when a is 1 (i.e., W is tetravalent) and b is 3 when a is 2 (i.e., W is trivalent) and Q is the SDA.
SSZ-53, as prepared, has a mole ratio of an oxide selected from silicon oxide, germanium oxide and mixtures thereof to an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof greater than about 20; and has the X-ray diffraction lines of Table 3 below. SSZ-53 further has a composition, as-synthesized and in the anhydrous state, in terms of mole ratios, shown in Table 2 below.
where Y, W, M and n are as defined above, c is 1 or 2; d is 2 when c is 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when W is pentavalent) and Q is the SDA.
SSZ-53 zeolites, as-synthesized, have a crystalline structure whose X-ray powder diffraction pattern exhibit the characteristic lines shown in Table 3 and is thereby distinguished from other zeolites.
After calcination, the SSZ-53 zeolites have a crystalline structure whose X-ray powder diffraction pattern include the characteristic lines shown in Table 4.
In addition to the peaks in Tables 3 and 4, there are peaks at 2 theta 22.0 and 21.6. These peaks may be partially overlapped with the peak at 2 theta 21.0, or appear as shoulders. Thus, the peaks at 2 theta 22.0 and 21.6 may be difficult to locate, especially if the SSZ-53 has a small crystal size.
SSZ-55 is disclosed in copending U.S. patent application Ser. No. 09/520,640, filed Mar. 7, 2000 which is incorporated herein by reference in its entirety. SSZ-55 is a zeolite having a composition, as synthesized and in the anhydrous state, in terms of mole ratios as follows:
YO2/WcOd 20-150
M2/n/YO2 0.01-0.03
Q/YO2 0.02-0.05
where Y, W, c, d, M and n are as defined above and Q is an SDA. SSZ-55 can be prepared from reaction mixtures shown in the table below.
where Y, W, a, b, M and n are as defined above and Q is the SDA.
SSZ-55 zeolites, as-synthesized, have a crystalline structure whose X-ray powder diffraction pattern exhibit the characteristic lines shown in Table 5 and is thereby distinguished from other zeolites.
After calcination, the SSZ-55 zeolites have a crystalline structure whose X-ray powder diffraction pattern include the characteristic lines shown in Table 6.
In preparing SSZ-59 zeolites, a N-methyl-N-[(1-phenylcyclopentyl)methyl]heptamethyleneiminium cation, N-methyl-N-[(1-(4-chlorophenyl)cyclopentyl)methyl]heptamethyleneiminium cation, N-methyl-N-[(1-phenylcyclopentyl)methyl]hexamethyleneiminium cation, N-methyl-N-[(1-(4-chlorophenyl)cyclopentyl)methyl]hexamethyleneiminium cation, N-methyl-N-((1-phenylcyclopentyl)methyl]piperidinium cation or N-methyl-N-[(1-(4-chlorophenyl)cyclopentyl)methyl]piperidinium cation is used as a crystallization template. In general, SSZ-59 is prepared by contacting an active source of one or more oxides selected from the group consisting of monovalent element oxides, divalent element oxides, trivalent element oxides, and tetravalent element oxides with the N-methyl-N-[(1-phenylcyclopentyl)methyl]heptamethyleneiminium cation, N-methyl-N-[(1-(4-chlorophenyl)cyclopentyl)methyl]heptamethyleneiminium cation, N-methyl-N-[(1-phenylcyclopentyl)methyl]hexamethyleneiminium cation, N-methyl-N-[(1-(4-chlorophenyl)cyclopentyl)methyl]hexamethyleneiminium cation, N-methyl-N-((1-phenylcyclopentyl)methyl]piperidinium cation or N-methyl-N-[(1-(4-chlorophenyl)cyclopentyl)methyl]piperidinium cation templating agent.
SSZ-59 is prepared from a reaction mixture having the composition shown in Table 7 below.
where Y, W, a, b, M and n are as defined above, and Q is the SDA.
SSZ-59 as prepared has a mole ratio of an oxide selected from silicon oxide, germanium oxide and mixtures thereof to an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof greater than about 20; and has, after calcination, the X-ray diffraction lines of Table 10 below. SSZ-59 further has a composition, as synthesized (i.e., prior to removal of the templating agent from the zeolite) and in the anhydrous state, in terms of mole ratios, shown in Table 8 below.
where Y, W, c, d, M and n are as defined above, and Q is the SDA.
SSZ-59 zeolites, as-synthesized, have a crystalline structure whose X-ray powder diffraction pattern exhibit the characteristic lines shown in Table 9 and is thereby distinguished from other zeolites.
Table 9A below shows the X-ray powder diffraction lines for as-synthesized SSZ-59 including actual relative intensities.
After calcination, the SSZ-59 zeolites have a crystalline structure whose X-ray powder diffraction pattern include the characteristic lines shown in Table 10.
Table 10A below shows the X-ray powder diffraction lines for calcined SSZ-59 including actual relative intensities.
Calcination can result in changes in the intensities of the peaks as well as minor shifts in the diffraction pattern. The zeolite produced by exchanging the metal or other cations present in the zeolite with various other cations (such as H+ or NH4+) yields essentially the same diffraction pattern, although again, there may be minor shifts in the interplanar spacing and variations in the relative intensities of the peaks. Notwithstanding these minor perturbations, the basic crystal lattice remains unchanged by these treatments.
The zeolites prepared by the present process are useful in hydrocarbon conversion reactions. Hydrocarbon conversion reactions are chemical and catalytic processes in which carbon-containing compounds are changed to different carbon-containing compounds. Examples of hydrocarbon conversion reactions include catalytic cracking, hydrocracking, dewaxing, alkylation, isomerization, olefin and aromatics formation reactions, and aromatics isomerization.
The following examples demonstrate, but do not limit, the present invention.